Purification of tetrachlorethylene



Patented Dec. 14, 1948 UNITED STATES PATENT OFFICE 2,456,184 PURIFICATION OF TETRACHLORETHYLENE' William C. Greenwald, Niagara Falls, N. Y assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application April 17, 1946,

. Serial No. 662,915

Claims. (01. zed-.654.

I This invention relates to a method for purifying and stabilizing tetrachlorethylene, which compound is also known as perchlorethylene. More particularly, it relates to a method for removing from tetrachlorethylene certain other chlorinated hydrocarbons which tend toimpair the stability of tetrachlorethylene and restrict its industrial applications. I a I I Tetrachlorethylene is used extensively in various industrial applications as a solvent in view ofits excellent solvent power for oils and greases. When pure, it possesses a high degree of stability and resistance to the action of heat, light, oxygen, water, etc.v However, when made by one of the more important methods used for its preparation, tetrachlorethylene is usually contaminated by small amounts of certain other chlorinated hydrocarbons notably 1,1,2-trichlorethane and asymmetrical (1,1,l,2-) tetrachlorethane which tend to.

reduce markedly the stability of tetrachlorethylene.

There are several well-known methods for preparing tetrachlorethylene. One of the more important of such methods utilizes acetylene and chlorine as basic raw materials. The method involves the chlorination of acetylene to form tetrachlorethane which is converted by dehydrochlorination to trichlorethylene. The latter compound is then chlorinated to produce pentachlorethane which is finally dehydrochlorinated to obtain the desired tetrachlorethylene according to the following equations: I

In actual practice of the above process, various side reactions occur in addition to the reactions The result represented by the above equations. is that the final product, although predominantly tetrachlorethylene, contains minor amounts of other chlorinated hydrocarbons, such as trichlorethylene boiling at 87 C., LIZ-trichlorethane boiling at114 0., asymmetrical tetrachlorethane stant boiling mixtures with tetrachlorethylene so as to make it practically impossible to separate completely these impurities by fractional distillation methods. I 7 Tetrachlorethylene-is also obtained as a valuable by-product of the process for producing trichlorethylene represented by reaction Equations 1 and 2 above. In the reaction to produce symmetrical tetrachlorethane (Equation 1) there isalso formed some pentachlorethane which, upon beingsubjected to dehydrochlorination, yields tend to decompose upon exposure tolight, heat,

moisture or oxidizing influences, with the formation of corrosive acidic decomposition products. The formation of suchdecomposition product-s renders the tetrachlorethylene corrosive to metal containers or metal equipment in which the tetrachlorethylene may be stored or used and makes the tetrachlorethylene' unfit for use in certain.

important applications. 1

The practical importance of eliminating asymmetrical tetrachlorethane and 1,1,2-trichlorethane impurities, from tetrachlorethylene is indicated by the large number of methods which have been proposed for the purification of tetrachlorethylene. Most of such methods involve treatments which change those impurities chemboiling at 129 C., pentachlorethane boiling at 159 C. and hexachlorethane boiling at 184 C.

The majority of such impurities may be separated from the desired tetrachlorethylene which boils at 121 C. by the usual methods of fractional distillation. However, two of the above impurities,

namely asymmetrical tetrachlorethane and 1,1,2-

trichlorethane not only possess boiling points within a few degrees of the-boiling point of tetrachlorethylene, but they also tend to form conically into derivatives which may be more readily separated from the tetrachlorethylene. Such treatments generally involve the use of costly chemicals and equipment and involve additional treatment steps which add appreciably to the cost of the purified product and complicate considerably the overall processing operations which are necessary.

It is. an object of my invention to provide a simple yet highly effective method for removing from tetrachlorethylene impurities, such as asym- The by-productmetrical tetrachlorethane and 1,1,2-trichlorethane. A further object is the provision of a practical method for purifying tetrachlorethylene and obtaining a more stable product. These and 4 lence in the countercurrently flowing streams. The methanol-water solution which was continuously removed from the top of the column contained substantial quantities of dissolved chlorostill further objects will be apparent from the 5 hydrocarbonswhile the tetrachlorethylene which ensuing description of the invention. was continuously removed iromthe bottom of My invention is primarily concerned with the thecolumn was relatively free from its starting purification 0i tetrachlorethylene obtained by impurities but contained some small quantities methods which involve the use of acetylene and of dissolved methanol and water. The rate of chlorine as basic raw materials. However, it mayflow of tetrachlorethylene through the column be utilized to purify any tetrachlorethylene which. varied between .18 to 50 cc./min. while the rate contains as impurities minor amounts of asymof flow of the methanol-water solution varied metrical tetrachlorethane or l-,l ,2-trichlorethane. between '70 to 140 cc/min. The effluent tetra- Accordingly, the above objects are accomplished chlorethylene was; dried and then tested to deterin accordance with the invention by subjecting mine'its stability and physical characteristics. tetrachlorethylene which contains. as; impurities The methanol-water solution from the top of the either one or both of the above compoundstdanv column was further processed to recover methextraction treatment using as the extracting anol therefrom. For comparative purposes, the liquid a mixture of an alcohol and water. Alcotests upon the purified tetrachlorethylene were hols which may be used are the butano1 .s, the duplicated employing the untreated crude tetrapropanols, ethanol and methanol. The extractchlorethylene.- I 1 ing liquid should contain suflicient water to Experience in testing perchlorethylenehas render it immiscible with the tetrachlorethylene. shown that a fairly good approximation of the The extraction may be carried out by any of the contents of asymmetrical tetrachlorethane' and. various well-known methods for extracting one 1,1,2-trichlorethane=-may be obtained by means liquid with another and may be accomplished ofafcaustic consumption test. Such-a test inbatchwise or continuously, volves refluxingfor 24 hours a mixture'of 50-00.

One efiective way of practicing the invention of tetrachlorethylene and 50 cc. 0.2 N'sodium hyinvolves flowing the impure tetrachlorethylene droxide solution'andat the end of that time down through an extraction column countercurtitrating the unconsumed sodium hydroxide in 1 rently to the fiowof, for example, a methanolcc. of the aqueous layerusinga 0.01- N hydrochlowater mixture. The tetrachlorethylenefrom ric acidsolution. The caustic consumed by 1 which impurities have been extracted is removed cubic centimeter of tetrachlorethylene is excontinuously from the-bottom of the'c-olumn and I pressed in terms of the number of cubic centia methanol-water solution containing dissolved 5 meters of-'0:0-l Nsoclium hydroxide solution equivtherein asymmetrical tetrachlorethane and 1,1,2-' alent thereto. The amount of caustic consumed trichlorethane which have been removed from the has been found to be roughly proportional to the tetrachlorethyleneare withdrawn'from' the top of amount of such impurities present in' the tetrathe column. The effluent-tetrachlorethylene from chlorethylene. The stability of tetrachlorethyl the extraction column may then be subjected 0' ene may be conveniently determined by refluxing to fractional distillation to removesmall quantia 125 cc. sample with 125cc. of water for 64 hours ties of water and methanol or may be merely and'then titrati'ng the aqueous layer with: 0:01 N subjected to a drying treatment after which it sodium hydroxide solution to determine the will be found that its stability'has been greatly amount'of'acidity developed. The results are eximproved. The water-methanol solution from 5 pressed in termsof the number of cubic centithetop of the column may be subjected to furmeters U N Sodium y o de q f t 0 ther. processing to recover methanol therefrom, the c y developed in 25 Of the q eou hi h may b mixed th t b quantity of layer. Such a test is usually carried out in the wat for reuse, presence of a weighed copper strip and after- The invention is further illustrated by the folthe test the strip i r weiehed to determine its lowing example: weight loss.

Example The effectiveness of the above extraction treatment in removin asymmetricaltetrachlorethane t t column ig of aiglass tubei I and 1,1,2-trichlorethane1 impurities is shown, by 25mm m and 64 hljgh wasrsecuFed the following data which. were obtainedby. test-: in a vert 11081111011 and filled with ""P ing the crude tetracl'ilorethyleneusedinthe aboverings. Crude tetreehlorethylene containing example by the standard tests described above and stantial quantities of asymmetrical tetrachloralso the purified tetrachlorethylene after it had ethane and 1,1,2-triCh10rethaI1e impurities s been subjected to the extraction treatment and continuously fed in at the top of the column then dried.

taisie t Caustic E2553? Sp. Gr. 15/40 iil li Acid Loss in Wt- 1st drop Last-drop Formae ofC'opper tiorr Strip', g.-

Prd tbf t u I a dfitat ifm tiofiiijiiii: 1233?? 13533 1:255 212. i 51: 3L??? while a stream of .a solution containing v .Itiis. obvious. from the above datathat the by volume of methanol and 10% ofwater was treated.tetrachlorethyl'ene is substantially purer continuously fed in at the bottomofi the column. andmuch more stable-than the untreated mate- The packing material in the columngserved to, rial. The improved purity of the treated prodincrease the contact. area. and to; provide turbu,= 7 5: uctl isindicated by its narrower boiling range and specific gravity as well as by the results of the caustic consumption tests. The improved stability of the treated product is shown by the fact that acid formation was almost negligible as compared with the development of an acidity equivalent to 212 cc. of 0.01 N sodium hydroxide solution per 25 cc. of the untreated sample. Also, the corrosion of copper was very much less after purification than before purification.

The methanol-water solution which is used to extract impurities from the tetrachlorethylene must contain sufficient water to render it immiscible with the tetrachlorethylene. Generally, quantities of water substantially less than about 5% by volume will be insufficient for this purpose. I prefer to use amounts of water corresponding to 5 to 15% by volume of the extracting liquid although good results may be obtained. using even larger amounts. However, as the quantity of water is increased beyond about 50% by volume, the effectiveness of the extracting liquid becomes so reduced as to render the use of such liquids impracticable. The preferred extracting liquid will consist of 5 to 15% water and 85 to 95% methanol by volume.

The extraction may be carried out effectively batchwise, but the countercurrent continuous method is generally more satisfactory for commerical purposes. Extraction is conveniently carried out at ordinary temperatures and pressures although operation at temperatures either above or below room temperature and at pressures either above or below atmospheric pressures may be employed if desired.

In commercial applications of the present invention, it will, of course, be advantageous to recover methanol from the methanol-water solutions containing the impurities which have been extracted. Since the chlorinated hydrocarbons which are removed by the extractin liquid form constant boiling mixtures with boiling points slightly lower than the boiling point of methanol, merely subjecting the methanol-water chlorohydrocarbon solution to fractional distillation is not entirely satisfactory. I prefer to dilute the mixture with about an equal part of water which generally results in the formation of a separate chlorohydrocarbon phase which may then be removed from the remaining water-methanol phase. The water-methanol phase may then be subjected to fractional distillation. The first fractions obtained upon such distillation will contain some chlorohydrocarbons in the form of constant boiling mixtures, but if the distillation is continued, a methanol fraction will be obtained which is relatively free from th chlorohydrocarbons. A practical way of utilizing the recovered fractions is to mix with those fractions first obtained the desired amount of water and methanol and feed the resulting mixture to the extraction column at about the middle of its height. The distillation fractions which are relatively free from chlorinated hydrocarbons may be mixed with additional quantities of methanol and water and fed to the bottom of the extraction column. By operating in this manner, most of the methanol may be recovered and reused so that the overall chemical cost of the purification treatment will be slight.

Ethanol may be used in the extraction liquid in place of methanol with good results. The propanols and butanols may also be used, but the employment of ethanol or methanol, particularly the latter, is more practicable and is preferred.

6 The quantity of water to be used will depend upon the particular alcohol employed, but in any case the amount should be sufficient to render the liquid immiscible with the tetrachlorethylene. Similarly, the maximum amounts of water that may be used withpractical results as well as the amounts which give optimum results will vary depending upon the alcohol chosen.

Various modifications may be made in the details and illustrations set forth above without departing from the spirit and scope of the invention. It is accordingly to be understood that the invention is not restricted to such details except as indicated in the appended claims.

I claim:

1. A method of removing impurities of the class consisting of 1,1,2-trichlorethane and asymmetrical tetrachlorethane from tetrachlorethylene comprising subjecting the impure tetrachlorethylene to an extraction treatment with a liquid which is immiscible with said tetrachlorethylene, said liquid comprising 50 to 95% of methanol and 5 to 50% water by volume.

2. A method of removing impurities of the class consisting of 1,1,2-trichlorethane and asymmetrical tetrachlorethane from tetrachlorethylene comprising subjectin the impure tetrachlorethylene to an extraction treatment with a liquid which is immiscible with said tetrachlorethylene, said liquid comprising to methanol and 5 to 15% Water.

3. A method of removing impurities of the class consisting of 1,1,2-trichlorethane and asymmetrical tetrachlorethane from tetrachlorethylene comprising intimately contacting impure tetrachlorethylene with a liquid while said impure tetrachlorethylene and said liquid are flowing countercurrently with respect to each other, said liquid comprising 50 to 95% methanol and 5 to 50% water by volume.

4. A method of removing impurities of the class consisting of 1,1,2-trichlorethane and asymmetrical tetrachlorethane from tetrachlorethylene comprising intimately contacting impure tetrachlorethylene with a liquid while said impure tetrachlorethylene and said liquid are flowing countercurrently with respect to each other,

said liquid comprising 85 to 95% methanol and- 5 to 15% water by volume.

5. A method of removing impurities of the class consisting of 1,1,2-trichlorethane and asymmetrical tetrachlorethane from tetrachlorethylene comprising continuously feeding the impure tetrachlorethylene to the top of an extraction column and a liquid comprising 85 to 95% methanol and 5 to 15% water to the bottom of said column, and continuously withdrawing a methanol-water solution containing said impurities dissolved therein from the top of said column and tetrachlorethylene from which said impurities have been removed from the bottom of said column. 3

WILLIAM C. GREENWALD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,084,937 Britton et al. June 22, 1937 2,120,668 Hanson et al. June 4, 1938 2,280,794 Cass Apr. 28, 1942 

